Process for conversion of a mixture of hydrocarbonaceous solids and liquid hydrocarbons



March 4, 1952 c; HUFF 2,587,729

PROCESS FOR CONVERSION OF A MIXTURE OF HYDROCARBONACEOUS SOLIDS ANDLIQUID HYDROCARBONS Filed May 51, 1946 2 SHEETS-SHEET 1 Patented Mar. 4,1952 PROCESS FOR CONVERSION OF VMJXTURE OF HYDROCARBONACEOUS SOLIDS ANDLIQUID HYDROCARBONS Lyman C. Huil", Evanstom'lll., assignor to UniversalOil Products Company, Chicago, Ill., a

corporation of Delaware Application May 31, 1946, Serial No. 673,506

This invention relates to improvements in the mining and processing ofhydrocarbonaceous solids, such as oil-saturated sands, tar sand,oilshale, bitumen or asphalt deposits, andthe like which may be found innatural beds and deposits. More particularly, the invention relates toimproved means for the high pressure hydraulic cutting of the solidmaterial from the bed and for hydraulically transferring the materialtoan improved processing operation which operates in combination with thehydraulic mining operation. The improved process employs the steps offlash distillation, drying, and coking or asphalting, all of which maybe carried onsimultaneously and continuously by means of alternatechambers.

In the mining and cutting operation, a bell or hood-like chamber, whichis open at the bottom, is used to enclose cutting nozzles and pumpingvmeans to remove the material cut away and. dislodged by the highpressure'streams or jets from the nozzles therein. The hood confines theliquid cutting agent and the removed solid material such that themixture is all removed and sucked away by pumping means which is alsowithin the chamber. A portable crane may be employed to handle the hoodand its internal hydraulic cutting and pumping apparatus such that itmay be moved from one spot to another over the entire bituminousdeposit.

A hot hydrocarbon solvent material is preferably used as the cuttingliquid in the mining operation and the solvent is also preferably anoilfraction obtained from the processing of the material being mined,however, steam,fhot water or other fluid may be employed under highpressure as the cutting medium and the fluidizing or transporting mediumfor transferring the solid material to the processing unit.

'I'he processing of the tar sands, following th aforementioned hydraulicmining operation, ,in one embodiment comprises briefly the steps ofthoroughly mixing the solid material and the cutting liquid or solvent,heating the mixture to a distillation temperature in a suitable heaterand passing it to a flashing and drying zone, flashing 01T the vaporousmaterial in said flashing zone, passing the flashed vapors to a rstfractionator and fractionating and condensing said vapors into desiredfractions, discontinuing the flashing operation in said flashing anddrying zones when the latter is substantially filled with heavy residueand mineral matter, passing a highly heated vapor stream into said zoneand subjecting the material therein to further dis- 1 Claim. (Cl.19e-56) tillation and drying, passing the resulting products of thehigher temperature distillation and drying operation to a secondfractionator` and therein fractionating saidV resulting productsl intodesired light, intermediate and heavy fractions, subjecting a portion ofthe;intermediate fractions to heating and recycling the heated fractionto said flashing and drying zone as the highly heated vapor stream foreffecting the higher temperature distillation and drying of residue insaid ashing and drying Zone, removing heavy bottoms material from thelower end of each said fractionators and coking said material inseparate chambers, withdrawing a portion of the intermediate fractionsfrom each of said fractionators and employing these last said fractionsunder pressure as the solvent material in the high pressurehydraulicmining operation` One of the important advantages of the processingoperation, comprising a portion of this invention, is the fact that theinitial distillation of the bituminous material can be carried out at arelatively low temperature and the light fractions thereby separatelyremoved without subjecting them to the destructive temperatures nec-.-essary in the second distillation and drying step. The improved processalso provides a period of digestion for the solidmaterial. Thisdigestion period occurs during the period in which the heavy residualmineral matter is being built up within the flashing and drying chamber,prior to the drying step. It has been found that the oil ofthe type heldwithin certain types of tar sands and the like, is susceptible to higheryields when there has been a digestion period at a moderatetemperatureand for a moderate period t of time.

In the processing of tar sands, there have been three principal methodswhich have been employed for the separation of the oil from the sand.One method has been the direct distillation of the solid material.Another has been the use of a solvent, such as naphtha, kerosene, or gasoil, to remove the oil from the sands, however, in practice it has beenfound that the solvent has had a greater ainity for the sand than hadthe original crude oil and the consequent loss of the solvent in thespent sand was unduly expensive. A third method for the separation ofthe oil from the sand is the use of hot water, however, this process hasmade necessary rather elaborate agitation and separation steps for removing the Water from the oil.

Various methods have been tried in the past and arev in use at presentfor theextraction o f solid bituminous materials, such as tar sands,which are removed from open pits. A shale planner has been used to someextent, but in general has been found to be rather unsatisfactory,particularly for the gummy types of tar sands. AV method which employsdynamiting, picking the material up by steam-shovel, and hauling it byVtractor to the processing plant has also been used, but this method hasbeen found to. be rather slow and expensive. In comparison, the miningmethod embodied in this invention is highly eiiicient and less expensiveto carry out. The hydraulic cutting provides easy and efficient meansfor cutting away and dislodging the material and the solvent is entireh'recovered by being pumped away with the dislodged solid material andreturned to the processing plant.

The features and advantages of the present invention will be moreapparent upon reference to the accompanying drawings and the followingdescription thereof.

Figure 1 illustrates diagrammatically the method of mining or removingthe solid bituminous material in combination with an improve( method ofprocessing the solid material to obtaii valuable hydrocarbon products.Various modiiications and alternative methods. of operation will bedescribed in connection with the description of the unit.

Figure 2 of the drawing shows a cross-sectional view through one form ofthe high pressure hydraulic jet cutting and pumping apparatus which isused to remove the solid carbonaceous material.

Figure 3 of the drawing is a cross sectional View through another formof apparatus having liquid jet nozzles, for high pressure cutting of thebituminous material and a Venturi-nozzle and liquid ejection stream toremove the liquid cutting agent and the dislodged solid material fromthe mining zone.

Referring now to Figure 1 of the drawing, there is shown a. movable typeof crane I which may be used to handle and move about the hydraulicmining apparatus 2 which is supported from a cable 3 at the end of theboom of the crane I. A liquid or solvent material to be used in thecutting apparatus 2 is supplied under high pressure through flexiblepiping yII which in turn connects with a supply line 5. The flexiblepiping 4 may comprise a number of short lengths of piping, withswivel-type joints between each section which are of a type particularlydesigned for high pressure service. The dislodged solid material and thecutting liquid, all of which is confined within the -hood or shell ofthe apparatus 2, is removed or pumped away from the apparatus through aflexa series of nozzles I 5 which discharge the medium in jet-like highpressure cutting streams, which in turn are directed angularly downwardsuch that the solid bed will be cut away and dislodged for removalwithin the area covered by the hood I0.4 Around the internal line I4,there is positioned a rotatable shaft I6 and an impeller blade I'Isuitable for a centrifugal type pump. The shaft I6 and the blade II maybe driven by a motor I8 which is supported in the upper portion of theapparatus. The housing I9 for the impeller blade I'I is supported fromthe shell II ible hose 6 that connects with a transfer line 'l which inturn communicates with a mixing tank 8.

'Io explain further the construction and operation of one specific formof the Ahydraulic mining apparatus 2, reference may be made to Figure 2of the drawing. The lower end of the apparatus comprises a circularhood-shaped section I0, which is open at the bottom and is adapted tolcontact the bed-on natural deposit of the bituminous material. Abovethe vhood I0 is a shell section II which serves as a shield andsupporting frame for the internal mechanical apparatus. The highpressure cutting liquid or solvent material is supplied to the apparatusby way of inlet line I2, at the upper end of the device. The fluidpasses through a swivel pipe joint I3 to an internal line or conduit I4which is centrally positioned and passes downwardly to .the lowerportion of the apparatus. Conduit I4 terminates in and connects directlywith the top of the hood I0 by way of the short connecting conduit 20,as indicated in the drawing. The centrifugal pump, provided by therotating blade I'I and the housing I9, draws the solid material, thathas been cut away, and the cutting liquid upwardly through the conduit20 and discharges it to the outlet line 2I. The outlet 2I may in turnconnect with ilexible piping or the hose 6, such as indicated in Figure1 of the drawing. A perforated plate or screen 22 is placed across theentrance of the inlet conduit 20 and serves to keep out any over sizedmaterial that would cause damage in being drawn through the centrifugalpump. The screen 22 may be attached to the conduit I4 and thus be madeto rotate with the conduit and discharge nozzles. In the apparatusshown, a system of gears is used in the box 23 above the motor I8I inorder to rotate the interior line I4 and the jet nozzles I5. However, inan alternate method of construction, the jet nozzlesv I5 may be placedat a slight angle such that the high pressure stream will cause theirrotation, and the gear box 23 may be eliminated. Above the pump housingI9, a supporting frame 24 is provided to carry the motor I8 and tofurnish attachment means for a yoke 25. The yoke 25 is provided with alifting eye at its upper end which makes the apparatus' adaptable for`handling by any type of hoist or moveable crane such as previouslyindicated.

In a somewhat simplified form of the cutting and pumping apparatus, asindicated in Figure 3 of the drawing, the centrifugal pump is eliminatedand in its place an ejector type of pump is used. High pressure liquidor solvent material enters the upper end of the apparatus through inlet26 and passes downwardly through the annular channel between an innerconduit 21 and an outer conduit 28. At the lower end of the annular flowchannel there are provided a plurality .of discharge nozzles 29 whichprovide high pressure jet streams for cutting away and dislodging thesolid bituminous material. An open bottom hood member 30 serves toconfine the cutting liquid and the dislodged solid material such thatboth may be removed by way of the internal pumping means provided. Theinner conduit 2T is provided with a Venturi-nozzle 3I at its lower endsuch that a high pressure jet stream of liquid from a centrally locatednozzle 32 will cause a jet pump action to draw the solids and liquidmixture upwardly therethrough into conduit 2'I and be dischargedtherefrom, through outlet line 33. A swivel type of pipe joint 34 isused between the upper end of conduit 21 and the discharge line 33 suchthat the apparatus may .be Yreadily moved about by means of a movable`crane or like equipment. The discharge nozzles 29 are preferably placedat an angle which will cause the conduits 21 and 28 to rotate from `thepressure of the jet streams and provide a full circular cutting actionon the solid material bed. Since it is desirable to rotate the 4nozzlesA2.9. the

inlet joint 26 and the outlet joint 34 must be of a swivel type ofconstruction as well as a type that will withstand high pressureservice. A perforated plate or screen 35 is positioned across the flaredinlet to the ejector or Venturi nozzle 3| in order to prevent itsclogging with large pieces of solid matter.

When employing a hydrocarbon solvent for the high pressure cuttingfluid, the bituminous material in the tar sands will be substantiallydissolved and removed from the mineral material by the time the mixturehas been pumped to the processing unit. vIn the preferable embodiment.of the combination process, an intermediate gas oil fraction, which isa product of the distilling process, is heated and passed to the miningapparatus as the hot solvent material.

In an alternate method of carrying out the mining operation, hot wateror steam may be used in the high pressure jets in the mining hood to cutaway the bituminous deposit and uidize the particles such that they maybe conveyed by pipe line to the processing unit. The passage 0f thewater and solids mixture directly to the distillation chambers, however,means the expenditure of considerable heat and energy in flashing olfthe large quantity of water present.

It is, therefore, advisable to remove the oil from f the water byemploying conventional settling basins, mixers, and skimming basinswhich have been used in connection with such types of material.

Referring again to Figure 1 of the drawing, the description of theprocessing unit, which is used in combination with the high pressurehydraulic mining method, will be continued. The solvent and solidsslurry, from the mining apparatus 2, is charged to the mixing tank 8byway of pipe line 1. The slurry mixed within tank 8 by means of blades36 so that the liquid solvent and solids material is thoroughly mixedprior to the heating and distillation steps. The mixture leaves the tank8 by way of line 31, having valve 38, and passesnthrough pump 39 whichprovides sufficient pressure to force the heavy material through line40, heating coil 4I in the heater 42, and be carried through line 43 toa series of distillation and drying chambers 44, 44 and 44". Thematerial is heated to a vtemperature of about 600 or 700 F. within theheater 42, such that the major portion of the lighter hydrocarbonfractions within the solids material, as well as the hydrocarbonsolvent, will be continuously flashed oil in a distillation operationwithin one of the distillation chambers. The material is charged by wayof one of the respective lines 45, 45 or 45, the flow being controlledrespectively by ,valves 46, 46 and 46'?. y

In order to lower the distillation temperature during this initialdistillation step and to further protect the light fractions againstexcessively high temperatures, super-heated steam may be introduced intothe transfer line 43 by way of line 41, having valve 48, or it may beintroduced directly to the distillation chambers by way of the`respective lines 49, 49' and 49, the flow being controlled respectivelyby valves 50, 50 and-50 -Three distillation and drying chambers, 44, 44and 44" are furnished in the preferable processying unit, such-asdiagrammatically illustrated in A,orderto provide for the continuous andsimulta- -`vneousoperation of all steps. chambers may be operated as aninitial iiash .,dstillaiogfchamber.. a-Second .as a, drying chamv Thus,one of the ber, while the third is having the coke and dried residualmaterial removed therefrom. One of the advantages of this improvedmethod of operation is the carrying out ofthe distillation and dryingoperations in two separate steps, so that a digestion period is obtainedduring the first step while heavy residual and mineral matter isbuilding up in the distillation chamber. As has been previously noted,with some types of bituminous materials, such as tar sands inparticular, it has been found that subjecting the material to heat for agiven period of time aids in effecting a higher recovery of oil from thesolid material,

The vaporized stream from the flash distillation' operation is passedfrom the particular distillation chamber being used, 44, 44 or 44", byway of line 5l, 5|' or 5|, having respectively control valves 52, 52 and52, to line 53 which in turn passes the vapors to the fractionator 54.The fractionator 54 operates to fractionate the vapors into desiredfractions or products, with `the lighter fractions being taken offoverhead by way of line 55, which will in turn carry the vapors tosuitable condensing and receiving apparatus. The heated stream of solidsand solvent is c ontinuously passed to one of the distillation chambersuntil it is substantially filled with heavy residual and mineral matter,the stream is then switched to a second distillation chamber which hasbeen cleaned and readied for use, and the filled chamber is thensubjected to a drying out operation. During the drying operation, theresulting vapors are passed from the drying chamber by way of line 56,56' or 56", the flow being controlled respectively by valves 51, 51 and51, to line 58 which in turn passes the material to the fractionator 59.In the fractionator 59 the vapors are fractionated into desired light,intermediate and heavy fractions, with the light overhead fractionsbeing carried by way of line 66 to suitable condensing and receivingapparatus. All, or a portion of the intermediate fractions which may becollected in centerwells within the fractionator 59, may be recycled tothe distilg lation and drying chambers 44, 44 and 44" with added heat,to effect the desired drying out operation. A kerosene fraction iswithdrawn from the fractionator 59 by way of line 6l having valve 62, oralternately a gas oil fraction withdrawn through line 63, having valve64 or a mixture of the two and the withdrawn fraction or fractionscharged by means of the pump 65, to a heating coil 66, in a heater 61.The recycle fraction yis heated to a temperature of the order of 900 to1000 F. in the heating coil 66 prior to its introduction into theparticular chamber 44, 44 or 44" which is effecting the drying outoperation. The hot -stream passes from the heater 61 by way of lines 68and 69, through control valvelll, to line 1I, 1l or 1|", havingrespectively control valves 12, 12' and 12, which in turn communicatewith the lower ends of each of the distillation and drying out chambers.The residual matter is thus stripped of all its volatile fractions andis substantially dried out to a cokelike material which may besubsequently removed, in a third step, by internally placed cables, orby other common methods of coke removal. When the residue has beensufficiently dried out, the hot drying out recycle stream is thenswitched to the chamber which has been effecting a ash distillation andis filling with residue. The drying out chamber may then be subjected toaction of Vsteam in order that the coke-like material may be more easilyremoved. During this steaming :out operation, the exhaust steam andentrained volatiles may be removed Lfrom the -upper portion of thechamber by means of line 13, 1-3 or '13, having respectively controlvalves 14, 14" and 14". This steam may be vented to the Aatmosphere -orpassed through la steam recovery and wash column, wherein somehydrocarbon `oil may be separated from the water.

The heavy bottoms fractions from each -of the fractionators 54 and 59 ispassed to suitable coking or asphalt producing chambers. `The heavymaterial from fractionator 54 passes b-yway of line 15, pump 16, line11, having valve 18, and

V'lines B4 and 84', to the coking chambers 19 and 19". The heavyresidual material from fractionator 59 passes by way of line 85, pump8l, and line v82, vhaving valve 83, to line 11, in order that it mayalso be charged to coke chambers 19 and 19'. The material is charged tothe coking chambers alternately however, such that one may be cleanedwhile the other is in operation. The flow 4from line 11 to the cokechambers 15 and #19 is by way of respective lines 84 and 84', which arerespectively controlled by valves 85 land 85. The

`vapors from 'the coke chambers pass by way of lines 86 and 35', havingthe respective `valves 81 and 81', to the fractionator 59 wherein Vtheyare fractionated together with the vapors from the drying out step. vAheated recycle oil fraction is also used within the coking chamber 19vand '19", vto aid in the drying out and coking operation therein. Thus,a portion of the recycled stream or heater 61 may pass by Way of lines68 and 88 or 88', to the lower end of the coking chambers, the ow beingcontrolled by the respective valves 89 and S9. l

If Vit is lfound desirable, asphalt products may be made from thefractionator bottoms within the Achambers 19 and 759. This may beaccomplished by providing steam and hot air for blowing the materialwithin the chambers. The steam may be supplied "to the chambers 11S and'19"' by way of lines 90 and S0", having the respective valves 0l andel', and heated air may -be supplied by way .of lines 92 and -$32',having` adjustmen't valves 93 and 93.

In another modification of the processing operation 'and apparatus, thecoking chambers 19 and -19 may be eliminated, in which case thefractionator bottoms will be passed to the distillation and 'drying .outchambers 44, 4t and `44". The .bottoms from fractionator 54 will ypassby way of line 15, pump 1t, line 11, line I.I5 and line IIB, H5' rorIIE", to the particular chamber effecting the drying out and cokingstep, the

ow being controlled respectively by valves lI I1, H1', and II1". Thebottoms from fractionator 59 will pass by way of line 80, pump l811 line82, line 11, having valve 18, and line H5, becoming mixed with .thebottoms from fractionator 54 ein' line II5, prior to reaching the dryingout chambers. In this operation the bottoms material is reduced to cokeat the same time rthe heavy residual and mineral matter is dried out.The Adrying out operation, Ias before, is carried out following theinitial fiash distillation .step and Athe building up of the residual.material 'in 'the chamber.

As previously noted, in the preferred embodin ment of the combinationprocess, an intermediate r oil fraction from fractionator'54 iswithdrawn from a center-well therein, and passed 'by way of line S4having control valve 55, to line '96, .91 and to line 5, which in turncarries the 'hot fractionto the mining apparatus 2 wherein it 'f8 used:as -a ihot solvent and cutting iiuid under high pressure, for effectingthe removal of a solid bituminous material. In alternate operations,fractions from the fractionator 59 may be used alone `as the hotsolvent, or used in combination with the intermediate fraction fromfractionator 54. Intermediate oil fractions may 'be withdrawn fromfractionator y59 through lines 93 and S9 having valves |00 and IUIrespectively, to transfer lines 56, which will in turn carry 'thematerial to pump S1 :and line 5. A heater 102 is provided for heating upthe solvent material when the unit is being started, so that a Vhotsolvent may be available for the mining vapparatus, or of course, theheater may be used to provide additional 'heat to .the fractionswithdrawn from the fractionators, where a higher temperature solvent isdesired than that which is obtained directly. The flow through theheater i512 may be obtained by closing 'valve A|03 inline 5 andswitching the material through line |04, having lvalve 105, to heatingcoil I0@ and thence to line lill, having valve H33, the latter `line linturnconnects with the transfer line 5. When solvent material `is notrequired in connection with the mining operation, it may be passed tosuitable place of storage. The material from fractionator 54 may betransferred to storage by way of line 54 and line IBS, havingfshu't-ovalve ii, while the Vmaterial in fractionator 59 may be passed tostorage by way of `lines 98 and 99 and the respective branch lines I I Iand I I2,hav

ing respectively shut-ofi valves I I3 Iand I I4.

It may be seen from the above description Vof the mining and processingoperations and the efficient combination of the two, that a means isprovided for recovering and transporting solid hydrocarbonaceousmaterial from their natural `deposits, such as tar sands and likematerials. Further, that the processing operation eiects the removal ofthe lighter hydrocarbon fractions without subjecting them to highdestructive distillation temperatures, While continuously con-v vertingsuch types of lhydrocarbonaceous materials into desired products, suchas gasoline, kerosene, diesel fuel, gas oiland coke or asphalt.

It should also be understood, that the invention is not limited to 'theexact forms of apparatus illustrated nor to the specific flow which hasbeen described.

The heaters and chambers of this processing unit may be operatedV atsubstantially atmospheric pressure .or at a superatmospheric pressure,from about 100 to 600 pounds per square inch, in which case, the actionof the `solvent would be increased and the 'bit'uminous'solids would besubjected to considerable decomposition and cracking, to thereby resultin the production of more valuable light products.

I claim as my invention:

A process for the pyrolytic conversion of a mixture ofrhydrocarbonaceous solid material and a fluid medium which comprisessubjecting said mixture to an elevated temperature under non-achingconditions, introducing the heated mixture into a fiashing Aand dryingchamber. dashing off 'lower boiling fractions from said mixture andpassing them to a first fractionator for fractionation and recovery ofdesired fracheated vapor I'stream through said residual 'material insaid chamber-and effecting a coking 9 and a higher temperaturedistillation thereof, passing vaporous products resulting from saidhigher temperature distillation and coking step to a second fractionatorand fractionating the same therein to produce desired light,intermediate and heavy fractions, heating a portion of the intermediatefractions from said second fractionator and recycling them to saiddrying chamber as the said heated vapor stream for effecting said highertemperature distillation and coking step, passing heavy fractionsfroinboth of said fractionators to a separate coking zone, passing aportion of said heated vapor stream through said heavy fractions in saidseparate coking zone, effecting coking of said heavy fractions and theremoval of vaporous porducts from said cokng zone, passing the last saidvaporous products to said second fractionator together with vaporousproducts from said drying chamber.

LYMAN C. HUFF.

l0 REFERENCES CITED The following references are of record in the le ofthis patent:

UNITED STATES PATENTS Number Name Date 1,418,098 Schneiders May 30, 19221,502,261 McArthur July 22V, 1924 1,778,515 Hampton Oct. 14, 19301,940,725 Morrell Dec. 26, 1933 1,963,265 Fisher et al June 19, 19342,075,599 Alther Mar. 30, 1937 2,146,790 Brewer Feb. 14, 1939 2,297,756Fender Oct. 6, 1942 2,386,036 R. Cross Oct. 2, 1945

